Process of producing fast dyeings and the dyed fiber obtained thereby



Patented Feb. 17, 19 42 A UNITED v STATES P PROCESS or PRODUCING FAST DYEINGS AND THE DYED FIBER. OBTAINED THEREBY Georg Krinzlein, Frankfort-on-the-Main, Werner Kirst, Konigstein in Taunus, Konrad Benn,

Frankfort-on-the-Main, and Wilhelm Seidenfaden, Ollfenbach-on-tbe-Main, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing.

Application February 26, 1941, Se-

rial No. 380,600. In Germany February 17, 1939 14 Claims.

The present invention relates to a process of producing fast dyeings and to the dyed fiber obtained thereby.

We have found that valuable dyeings of good properties of fastness are obtained on animal fibers and on natural or artificial cellulose fibers as well as on mixtures of animal fibers with cellulose fibers and furthermore on foils by applying to the material to be dyed a compound derived from 1.3.5-triazine and containing either the diazotization process.

radicals may be used.

process are substantive.

and ethers.

fastness may be improved.

terials may, for instancabe prepared as described in German patent specification No. 485,185.

The following examples serve to illustrate t e invention, but they are not intended to limit it thereto. v

(l) 1 kilo of mixed yam consisting of 50 parts of wool and 50 parts of staple fiber from viscose is treated for 1 hour at 85 C. in a bath containing per 24 liters of water 40 grams of the compound obtained by reducing the tertiary condensation product from cyanuric chloride, 1 mol of 2-amino-5-naphthol-'l-sulfonic acid, 1 mol of 5-nitro-2-aminophenol and 1 mol of aniline, of at least one substituted or unsubstituted radical the following formula which contains an amino-group capable of being NH! diazotized and at least one radical capable of coupling with diazo-compounds, or a radical which contains simultaneously the amino-group l5 capable of being diazotized and .the position capable of coupling with diazo-compounds, as well as at least one group lending solubility in water, NH then diazotizing the compound and causing it to combine with itself. The self-coupling may be performed or completed, for instance, by adding 1 to the diazo-bath an agent neutralizing the acid Confirm-(K or having an alkaline action, after the diazotization is finished, or'by passing the goods through a bath having an alkaline action subsequently to H The radical containing the amino-group 021- d 0 grams of amlnomumsulfate. 6 B pable of being diazotized a d th di of sodium sulfate, dissolved in 6 hters of water, pable of coupling with diazo-compounds may be are then added and the material is further linked to the triazine radical by a carbon-, oxytreated for 1191f l 110111 at 70 It s then gen-, nitrogenor sulfur-bond, rinsed, diazotized 1 n the cold for half an hour As radicals capable of coupling it diam? in a solution conta ning per 30 liters of water 25 compounds there may be mentioned, for instance, grams of s d u mtrlte. 25 a s of s dium dithe radicals of naphthols, of ortho-hydroxycarbuty t e sulfopate and 75 of oboxylic acids, of beta-ketocarboxylic acids, of 2- chloric acid of 20 Be. 'lhe material is then amino-5-naphth 1-7- 1f0 i a id, of 2 i 3 treated for half an hour in a fresh bath connaphthol-G-sulfonic acid, of 1-amino-8-naphtaming D 30 liters of cold Water 75 of thol-3.6-disulfonic acid,'of 1-amino-3-dimethylmonia f 25 p t s th and 0 rams of aminobenzene or of pyrazoloneg, As further the condensation product from 1 mol of octoderadicals the most various. inorganic or organic 40 0371841001101 and 20 111015 of ethyleneoxide. rinsed and dried. A leather-brown dyeing of good prop- Most of the compounds used in the present erties of fastnessisobtained.

Owing to the 'substan- When this dyeing is after-treated for one hour tivity of these compounds it is possible to obtain at 95 C. with a Solution Containing P liters on cellulose and regenerated cellulose as well as of water 20 grams o Potassium bichl'omate and on mixtures of these fibers with animal fibers 0 00. of fo mic ac d o 35 P8 cent Strength, and, furthermore, on sheets from regenerated deeper leather-brown tint of very good properties cellulose dyeings which are distinguished by their of fastness is obtained. good properties of fastness. As far as the con- When the above leather-brown dyeing, diazodensation products do not contain a sulfonic acid timed and developed with ammonia, is aftergroup, they have an afiinity for cellulose esters treated for one hour at C. with 20 grams of By treating the dyeings on the fiber copper sulfate and 10 cc. of acetic acid of 50% with agents yielding metal, their properties of strength, a greenish leathe w tint of q y good properties of fastness is obtained.

The condensation products used as parent ma- 6 2) 1 kilo of wool is treated for 90 minutes at C. with a solution containing per 30 hters of water 40 grams of the compound obtained by reducing the tertiary condensation product i'rom cyanuric chloride, 1 mol of 2-amino-5-naphthol- 7-sulfonic acid, 1 mol of 5-nitro-2-amino-1- methoxybenzene and 1 mol of aniline, with addition of 80 grams of ammonium sulfate, 100 grams of sodium sulfate and 5 grams of the condensation product from 1 mol of octodecylalcohol and 20 mols of ethyleneoxide. The material is then rinsed, diazotized for half an hour with a. solution containing per 30 liters of cold water 25 grams of sodium nitrite, 75 cc. of hydrochloric acid of 20 Be. and 25 grams of sodium dibutylnaphthalenesulfonate, and developed for half an hour in the cold with '15 cc. of ammonia of 25% strength in 30 liters of water. Finally the material is rinsed. A bluish Bordeaux dyeing is obtained whose good properties of fastness may be essentially improved by treating it in the heat with chromium or copper salts.

(3) 1 kilo' of mixed yarn consisting of 50 parts of wool and 50 parts of staple fiber from cuprammonium cellulose is treated for one hour at 80 C. with a solution containing per 30 liters of water 40 grams'of the compound obtained by reducing the tertiary condensation product from cyanuric chloride, 1 mol of 2-amino-5-naphthol- 7-sulfonic acid, 1 mol of 5-nitro-2-naphthylamine and 1'mo1 of aniline, and 600 grams of sodium sulfate. The material is further treated for 30 to 45 minutes at a temperature falling to 65 0.," rinsed and diazotized for half an hour with a sulfate. The material solution containing per 30 liters of cold water 25 grams of sodium nitrite and 75 cc. of hydrochloric acid of 20 B. Thereupon the material is developed for half an hour in a fresh bath containing per 30 liters of cold water '15 cc. of ammonia of 25 per cent strength and 5 grams of the condensation product from 1 mol of octodecyialcohol and 20 mols of ethylene oxide,- rinsed and dried. A garnet dyeing is obtained.

densation product from cyanuric chloride, 1 mol of 1-amino-8-naphthol-3.6-disulfonic acid, 1 mol of s-nitraniline and 1 mol of aniline, 80 grams of ammonium sulfate and 600 grams of sodium is further treated for 45 minutes at a. temperature fal to q, rinsed and diazotized for half an hourwith a solution containing per'30 liters of cold water 25 grams of sodium nitrite and '75 cc. of hydrochloric acid of 20 B. Thereupon the material is treated for half an hour in the cold in-a bath containing per 30 liters of water about cc. of amis obtained. By an after-treatment with metal salts bluer tints with improved properties of fastness are obtained, When the yarn contains effects from acetate silk, these efiects are reserved.

(5) 1 kilo of a mixture consisting of 50 parts of wool and 50 parts of acetyl cellulose is treated for-one hour at Gil-70 C. in 30 liters of a bath containing 50 grams of a condensation product of the following formula (obtainable by condensing cyanuric chloride with 2 mols of 2-acetylamino-5- (benzenesulfonyloxy) naphthalene-'Z-sulfamide, subsequently saponifying the acyl groups by-means of alkalies and exchanging the third chlorine atom for the hydroxyl group),- grams of ammonium sulfate and 200 grams of sodium sulfate. The material is then centrifuged, diazotized for half an hour in a bath containing per 30 liters of water' grams of sodium nitrite and 240 cc. of hydrochloric acid of 20 1%., further treated for 10 minutes in a bath containing in 30 liters of water cc. of ammonia of 25% strength, rinsed and dried. ,A currant dyeing is obtained.

6) 1 kilo of a sheet consisting of acetyl cellulose is trea for one hour at 60 C. with 50 grams of the condensation product described in Example 5. The material is then squeezed, treated for half an hour in '30 liters of water containing 90 grams of sodium nitrite and 240 cc. of hydrochloric acid of 20 36., squeezed again and developed for 10 minutes in 30 liters of water containing 150 cc. of ammoniaof 25% strength, rinsed and dried. 'A currant dyeing is obtained. The following table illustrates the shades of a number of other dyeings obtainable by self-cou- I pllng according to the present invention:

Parent component Shade Condensation rodn'ot from 1 niol of no with subsequent reduction.

2-hydroxyto uene dynamic chloride, 1 mol oi 2-amino-8-nsphthol-6-suli'onic acid, 1 mol of s-nitrsniline and Condensation ]product from cyanurie chloride, 1 mol of 21mino-5-naphtliol-7-sulfonic acid 1 mol of 5-nitro-3-aminoand 1 mol of aniline with subsequent reduction, corresponding with Van bluish red; after-treated with anetal salts: Borthe formula:

m e t a1 a a I t s: brown.

benzene-HulIamide with subsequent alkaline saponiflcation oi the acetyl group and exchange or the third chlorine atom (or the hydroxyl group, corresponding with the iormula:

OH N/ NH:

\ Parent component Shade V 3 Condensation product from cyanuric chloride, 1 mol of 2-amlno-5-naphthol-7-sul ionic acid, 1 mol of {-nitro-2-amino- BrownishBordeaux. anisole and 1 mol oi aniline with subsequent reduction, corresponding with the formula: 7

CHaQ

I-|IH l i mHQ-NH-c C--NH sour 4 Condensation product from cyanuric chloride, 1 mol of Z-amino-5-naphthol-7-sulionic acid, '1 mol of 4-nitraniline and Bordeaux.

1 mol of aniline with subsequent reduction. 5 Condensation product from cyanuric chloride, l'mol of 2-amino-S-naphthoi-T-sulfonic acid, 1 mol of flrnitraniline Red.

and 1 mol of aniline with subsequent reduction. 6 Condensation product from cyanuric chloride, l'moloi 2-am1no5-naphthoI-7-sulfonlc acid, 1 mol of 4-nitrophenol-, S carl et; a i t erand 1 mol of aniline with subsequent reduction, corresponding with the formula: chromed: yellowish red; altertreated with copper salts: brownorange. v NH:

| i ii CeH5.NH-C C-NH -5021! 7 Condensation product fronncyanuric chloride, 1 mol of ?-amino-5-naphthol-7sulfonic acid, 1 moloi 5-amino-3-nitro- Leather-brown; al-

2-hydroxy-benzoic acid and 1 mol of aniline with subsequent reduction. a a ter-treated with I copper salts: leather-brown. 8 Condensation product from cyanuric chloride, 1 mol of 2.3-hydroxynaphthoic acid amide and 1 mol oi1-amino-4-ace- Bluish red.

tylaminobenzene with subsequent alkaline saponification of the acetyl group and exchange of .the third chlorine atom for the hydroxyl group, corresponding with the formula:

(|)H n v N c O.NHC C-NH-O-NH:

9 Condensation product from cyanuric chloride, 1 mol of 2.3-hydroxynaphthoic acid amide, 1 mol of l-amino-4-ace- Bordeaux.

tylamlno-2.5-diethoxybenzeue and 1 mol of l-ammobenzene-tsulfomc acid with subsequent alkaline saponiflcation oi the acetyl group, corresponding with the formula: I

OH 0 CzHs I C ONE-('3 ("J-NH N H:

\ CaHs NH 8 O Na t 10 Condensation product from cyanuric chloride, 1 mol of 2.3-hi droxynaphthoic acid amide and 1 mol of l-acetylamino- Yellowish red.

4 I amen? Parentcomponent Shade ll Condensation product from cyanurio chloride, 1 mol of 23-h dro xgnaphthoic acid amide, 1 mol of l-aoetylamlno- Yellowish led. v benzene-Zemfamide and 1' mol of i-aminobenzene-Hulfo cl with subsequent alkaline seponiflcation of the acetyl group, corresponding with the formula:

0H NH:

N CO.NE-C/ E-Nn-so f/ NH S 0 INS 4-ecetylaminobenzene and 1 mol oi sulfanilic acid with subsequent saponiflcstion of the acetyl group, corresponding NH SOzNa 13 Condensation roduct from cyanuric chloride, 1 mol of 1-(4'-amin0phenyl)-3-methyl-5-grazolone, 1 mol of l-nitro Yellow. benzene-asulfamide and 1 mol of l-eminobenzene-i-sulionio acid with subsequent r v uction of the nitro-grou corresponding with the formula: v p

om-co N \NONHkC c-NH-sm-O N I l om c OaNa 14 Condensation product from c anuric chloride, 1 mol of 2-amino-5-hydroxynaphthaiene-7-sulfonylwyclohexylamine, Yellowish red.

lmol of 1-n.itrobenmnefamide and 1 mol oi l-aminobenmne-Hulionic acid with subsequent reduction of the nitro-aroup, corresponding with the formula: 1

m1, I K C @NH-SO NH-C c-mr-so 1k 2 c a 1 m 18 Condensation roduct from anurio chloride 2 mole of Z-acetylamino-5-(benzeneeulfonyioxy)-naphthalene-7- Reddish blue.

suliamide an 1 mol of l-amin benzenmulfonic acid with subsequent splitting oil of the acyl groups, correspondin: with the formula:

12 Condensation product from cyanurlc chloride, 1 mol of 1-(4-aminophenyl)-3-methyi-5-pyrazclone, 1 mol of 1-amin Brownish yellow.

Shade Condensation product from cyanurlc chloride and 2 mole of 2- groups, corresponding with the formula:

mN-Oc 0.1m

. 7-su1fonic acid, 1 mol of 1-amino-4-acetylaminobenzene and 1 mol nN-IciO I' no naphthalene-'I-srfilamide with subsequent reduction of the nitro-g'roups and alkaline saponification of the acyl OII Condensation product from cyanuric chloride, 1 mol of 3'-amino-C-phenyl-1.2-(N)-imidazolo-5-hydrorynaphthalenequent splitting ofl oi the acetyl group, corresponding with the following formula:

Condensation product from cyanuric chloride, 1 mol of 2-acetylamino-fi-(benienesulfonyloxy)-naphthalene-7- sulfamide, lmol of 2.3-hydroxynaphthoic acid amide and 1 mol of 1-am1no-4-acetylaminobenzene with subsequent saponiflcation of the acyl radicals, corresponding with the following (4-nitrobenzoylamino)-5-(benacnesulfonyloxy)- Bluishred.

NrLoo-O-Nm subdued red. of l-amlnobenzene-4-sulionlc acid with subsef Bluish red.

formula We claim:

1. Process of producing fast dyeings on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers, which comprises applying to the fiber a compound derived from 1.3.5-triazine containing a. group lending solubility in water, a diazotizable amino group and a grouping which is capable of coupling with a diazo compound, then diazotizing the compound on the fiber and causing self-coupling by an alkaline treatment.

2. Process of producing'fast leather-brown dyeings on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers, which comprises applying to the fiber the compound obtained by reducing the condensation product from cyanuric chloride, 1 mol of 2-amino-5-naphtho1- 'Z-sulfonic acid, 1 mol of -nitro-2-aminophenol and 1 mol of aniline, corresponding with the following formula:

on t me C l CeHaNH-C 0-NH then diazotizing the compound on thefiberand causing self-couplingby an alkaline treatment 3. Process of producing fast leather-brown dyeings on fibrous material of the group consisting then diazotizing the compound on the fiber, causing self-coupling by an alkaline treatment and treating the dyeing with an agent yielding metal.

4. Process of producing fast leather-brown dyeings on fibrous material of the, group consisting of cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers, which comprises applying to the fiber the condensation product from cyanuric chloride, 1 mol of Z-amino- 5-naphthol-7-sulfonic acid, 1 mol of 5-nitro-3- amino-2-hydroxytoluene and 1 mol of aniline 3 with subsequent reduction, corresponding with theformula:

' then diazotizing the compound on the fiber and causing self-coupling by an alkaline treatment.

,5. Process of producing fast brown dyeings on fibrous material oi the group consistingrof cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers. which comprises applying to the fiber the condensation product'from cyanuric chloride, 1 mol of 2-amino-5-naphtholdroxytoluene and 1 mol of aniline withsubsequent reduction, corresponding with the formula:

Hi NH:

SOaH

' then the compound on the fiber, causing selbcoupling by an alkaline treatment and treating the dyeing with an agent yielding metal.

6. Process of producing fast leather-brown dyeing: on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures at animal fibers with cellulose fibers, which com.- prlsea applying to the fiber the condensation product from cyanuric chloride; 1 molof 2-aminofi-naphthol l-sulionic acid, 1 mole! 5-amino-3- nitro-2-hydroxy-benzoic acid and 1 mol of anie line with subsequent reduction, corresponding with the formula:

- H000 NH:

A If N mama-c t-ss then diazotizing the compound on the fiber and causing sell-coupling by an alkaline treatment.

'7. Process of producing fast leather-brown dyeings on fibrous material of the group consisting of cellulose fibers, animal fibers and mixtures of animal fibers with cellulose fibers, which comprises applying to the fiber the condensation product from cyanuric chloride, 1 mol of 2-amino- 5-naphthol-7-sulfonic acid, 1 "mol of 5-amino-3- nitro-2-hydroxy-benzoic acid'an-d 1 mol of aniline with subsequent reduction, corresponding with then diazotizlng the compound von the fiber, causing self-coupling by an alkaline treatment and treating the dyeing with an agent yielding metal.

8. Fiber dyed with an azo-compound obtainable on the fiber by the process claimed in claim 1. 9. Fiber dyed with an azo-compound-obtainable on the fiber by the process claimed in claim' 2. 

